The Asian region is one of the major emission sources of air pollution. Although ambient PM2.5 has been linked to several health risks in high-, low-, and middle-income countries, the further analysis of type impact is still rare but significant. The PM2.5 distribution retrieved from MODIS (Moderate Resolution Imaging Spectroradiometer) aerosol optical depth products within 16 years thus explored the associations between under-five and maternal mortality for 45 countries in Asia. Both the nonparametric (Generalized Additive Mixed-Effect) and parametric (Generalized Linear Mixed-Effect) models were employed to analyze the collected datasets. The results show that the levels of PM2.5 in Asian sub-regions were higher than the Global Air Quality Standards. Biomass PM2.5 concentrations was associated with increased the rate of under-five (Incidence Rate Ratio, IRR = 1.29, 95% CI, 1.13–1.47) and maternal (IRR = 1.09, 95% CI: 1.08–1.10) deaths in Asia. Anthropogenic PM2.5 was associated with increased rate of under-five deaths in Asia by 12%. The nonparametric method revealed that dust PM2.5 was positively associated with the under-five (β = 0.04, p < 0.001) and maternal (β = 0.07, p < 0.001) deaths in Asia. The rate of maternal deaths was increased by biomass/dust (IRR = 1.64, 95% CI: 1.63–1.65) and anthropogenic/dust (IRR = 1.22, 95% CI: 1.19–1.26) mixture types. In description, long-term exposure to different types of ambient PM2.5 in high concentration increased the rate of under-five and maternal deaths, suggesting that policies focusing on preventive and control measures is imperative for developing an improved maternal, newborn, and child health in Asia.